EP0552331A4 - - Google Patents
Info
- Publication number
- EP0552331A4 EP0552331A4 EP19920915405 EP92915405A EP0552331A4 EP 0552331 A4 EP0552331 A4 EP 0552331A4 EP 19920915405 EP19920915405 EP 19920915405 EP 92915405 A EP92915405 A EP 92915405A EP 0552331 A4 EP0552331 A4 EP 0552331A4
- Authority
- EP
- European Patent Office
- Prior art keywords
- halide
- phenol
- bisphenol
- oxidation state
- polycarbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
- C08G64/307—General preparatory processes using carbonates and phenols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/02—Preparation of carboxylic acid esters by interreacting ester groups, i.e. transesterification
Definitions
- the present invention relates to a process for the preparation of polycarbonates. More particularly, the present invention allows for the preparation of polycarbonates via an
- Suitable catalysts for the transesterification reaction include alkali metal salts such as lithium hydroxide, lithium phenate, bisphenol-A dilithium, etc. Suitable temperatures for the reaction are from 150 to 380"C.
- the initial polycarbonate produced in accordance with transesterification step A is generally a relatively low molecular weight oligomer having from 5 to 15 repeating units. This low molecular weight prepolymer can be advanced to a higher molecular weight polymer by merely heating the prepolymer.
- solid state advancement Anothertechnique for increasing polymer molecular weight, known as "solid state advancement", utilizes prepolymer which has been converted to a crystalline state. This latter technique is disclosed in US-A- 4,948,871. Both processes produce additional quantities of phenol which may be separated from the polymer and recycled to step C.
- the separation of phenol and polycarbonate is relatively simple especially under the preferred operating conditions ofthe present invention where substantially no solvent is utilized. Generally the phenol is distilled from the mixture, optionally at reduced pressure to insure complete removal of phenol.
- step C the phenolic compound and carbonyl halide are contacted at elevated temperatures in the presence of a catalyst.
- a catalyst Either homogeneous or heterogeneous catalysts may be employed.
- homogeneous catalysts include metal phenates, tetramethyl ammonium halides, aromatic heterocyclic basic nitrogen compounds, salts or adducts thereof and hydroxy substituted pyrid ⁇ nes.
- heterogeneous catalysts are Lewis acids or transition metal compounds that generate Lewis acids, supported metal salt catalysts, and aluminum trif luoride. This step ofthe process may be illustrated schematically bythe following diagram: 2 Ar ' OH + C0C12 ⁇ (Ar * 0 ) 2 C0 + 2 HCI
- the phenol recycled from step B supplies at least 95 percent, more preferably at least 99 percent of the phenol reactant for step A.
- Preferred carbonyl halides for use in the present process are phosgene, bromophosgene and mixtures thereof.
- a most preferred carbonyl halide is phosgene.
- Aryl haloformates which may be thought of as the intermediate product resulting from reaction of the carbonyl halide and 0 the phenolic compound may also be prepared bythe process. They may be separated from the desired diaryl carbonate and recycled by contacting with the same or another phenolic compound in one embodiment of the present invention.
- a desirable mole ratio of the phenolic compound to the carbonyl halide is 1 : 1 to 3: 1. Higher ratios of carbonyl halide relative to the phenolic compound result in larger amounts of aryl 5 haloformate being formed. Preferred molar ratios of phenolic compound to carbonyl halide are from 1.8: 1 to 2.1 :1.
- reaction for step C employs temperatures from 25°Cto 450°C, preferably
- the process is desirably carried out using phosgene under either liquid or gaseous reaction conditions. Pressures from 0.01 atm (1 KPa) to 50 atm (5 MPa) may be used, 0 with pressures from 0.1 atm (10 KPa) to 5 atm (500 KPa) being preferred. Inert diluents such as nitrogen, toluene, carbon dioxide, etc. may also be present if desired.
- the preferred method uses homogeneous catalysts, especially AICI 3 , temperatures from 120 to 150°C, and no solvent, that is, neat reaction conditions.
- step C can be carried out in any suitable reactor including a fixed bed reactor, a fluidized bed reactor or a circulating fluidized bed reactor, in which case the catalyst desirably is utilized as a fluidizable powder.
- Desirable residence times in such reactors are from 1 to 3000 seconds. Preferred residence times are 1 to 60 seconds. Most preferred are residence times of 1 to 10 seconds.
- Materials of construction must be resistant to the highly corrosive carbonyl halide. Suitable materials are glass, glass lined steel and HastalloyTM.
- periodic regeneration of the catalyst can improve the conversion rate of starting materials to product. Regeneration is accomplished by treating the catalyst with methanol or water at an elevated temperature in the range of 400°C to 600°C.
- a hydrogen halide byproduct is also formed in step C. This may be recycled, sold or utilized in other processes. In a preferred embodiment the hydrogen halide byproduct is reconverted to a carbonyl halide and reused in the process.
- One technique for this procedure uses metal Redox swing reactors or other suitable system to convert the hydrogen halide to halogen. In the metal Redox swing process, two reactors or two separate regions of a single reactor are employed to alternately convert the hydrogen halide produced from step C to a high oxidation state metal halide by contacting the same with a low oxidation state metal halide in the presence of an oxidant.
- a preferred metal Redox pair for such a swing reactor system is the copper(l)/copper(ll) chloride system.
- copper(l) chloride is converted to copper(ll) chloride by reaction with hydrogen chloride and an oxidant.
- Water is the sole byproduct ofthe reaction.
- the preferred oxidant is an oxygen containing gas, especially air.
- the preferred reaction conditions for converting the hydrogen halide to the corresponding high oxidation state metal halide are temperatures of 100 to 500°C and pressures from atmospheric (100 KPa) to 10 atmospheres (1 MPa).
- copper(ll) chloride is converted to copper(l) chloride by reacting copper(ll) chloride with carbon monoxide to form phosgene.
- the preferred reaction conditions for regenerating the low oxidation state metal halide are temperatures from 50 to 500°C and pressures of carbon monoxide from atmospheric (100 KPA) to 10 atmospheres (1 MPa). The net reaction isthe conversion of hydrogen halide and carbon monoxide to carbonyl halide and water.
- an oxygen sensor may be utilized such that upon sensing imminent breakthrough of oxygen from the bed used for conversion ofthe metal from low oxidation state to high oxidation state, the direction of flow in the swing reactor is reversed.
- a carbon monoxide detector at the exit of the reduction bed can be used to signal when to reverse the flow ofthe swing reactor.
- step C reacting a carbonyl halide with at least some ofthe phenol from step B to produce a hydrogen halide and a diaryl carbonate, and recycling the diaryl carbonate to step A;
- step D contacting at least some ofthe hydrogen halide produced in step C with a low oxidation state metal halide and an oxidant to generate water and the corresponding high oxidation state metal halide;
- step D on or before exhaustion ofthe low oxidation state metal halide, contacting carbon monoxide with the high oxidation state metal halide formed in step D to generate carbonyl haiide and regenerate the low oxidation state metal halide;
- polymerization reactor 8 via line 7, and phenol byproduct from step A is removed via line 5 and supplied with necessary make-up phenol to primary reactor 1.
- Bisphenol is supplied to polymerization reactor 8, via line 10.
- the desired polycarbonate is removed via line 6, and may be further advanced to higher molecular weight if desired.
- Hydrogen halide product from step C is routed via line 9, to one of twoswing reactors, 1 1 and 12. Inside the reactor 1 1, is a layer
- the carbonyl halide is discharged to the primary reactor via line 3.
- the layer, 13, is capable of absorbing oxidant should a slight break 0 through into the layer occur.
- the operation of the twin swing reactors changes.
- the reactor that before had converted hydrogen halide is regenerated while supplying carbonyl halide to the primary reactor, and vice versa.
- the present system allows for the overall conversion of a 5 bisphenol to the corresponding polycarbonate utilizing a carbonyl halide.
- Byproduct hydrogen halide can be reconverted to carbonyl halide using carbon monoxide and oxygen reactants. This essentially eliminates the requirement of purchasing, storing, handling and using halogen forthe preparation of carbonyl halides for use in the production of polycarbonates.
- the recycle of phenol and optional captive use of hydrogen halide and carbonyl chloride allows for 0 great economy and simplicity in the resulting process.
- substantially no solvents other than the recited reactants are utilized in the various steps.
- the polymerization is conducted under molten conditions such that no solvent needs to be separated from the phenol byproduct.
- no liquid/aqueous waste products are produced as in the conventional 5 solution or interfacial processes forthe production of polycarbonates. This allows for a process with significantly improved environmental impact.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Polyesters Or Polycarbonates (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US07/741,925 US5189139A (en) | 1991-08-08 | 1991-08-08 | Preparation of polycarbonates comprising separating bisphenol, converting bisphenol to diaryl carbonate and recycling |
US741925 | 1991-08-08 | ||
PCT/US1992/005800 WO1993003084A1 (en) | 1991-08-08 | 1992-07-10 | Process for the preparation of polycarbonates |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0552331A1 EP0552331A1 (en) | 1993-07-28 |
EP0552331A4 true EP0552331A4 (en) | 1994-02-09 |
EP0552331B1 EP0552331B1 (en) | 1996-05-29 |
Family
ID=24982794
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92915405A Expired - Lifetime EP0552331B1 (en) | 1991-08-08 | 1992-07-10 | Process for the preparation of polycarbonates |
Country Status (10)
Country | Link |
---|---|
US (2) | US5189139A (en) |
EP (1) | EP0552331B1 (en) |
JP (1) | JP3260369B2 (en) |
KR (1) | KR100214904B1 (en) |
CN (1) | CN1069740A (en) |
AT (1) | ATE138671T1 (en) |
CA (1) | CA2092288A1 (en) |
DE (1) | DE69211113T2 (en) |
ES (1) | ES2087545T3 (en) |
WO (1) | WO1993003084A1 (en) |
Families Citing this family (20)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5189139A (en) * | 1991-08-08 | 1993-02-23 | The Dow Chemical Company | Preparation of polycarbonates comprising separating bisphenol, converting bisphenol to diaryl carbonate and recycling |
DE4240314A1 (en) * | 1992-12-01 | 1994-06-09 | Bayer Ag | Prepn of polycarbonate(s) by melt esterification, by degrading polycarbonate from di:phenol - using quat. ammonium or phosphonium cpd as catalyst, prepn. of oligo:carbonate and polycondensation |
US5498319A (en) * | 1993-06-29 | 1996-03-12 | General Electric Company | Process for purifying diaryl carbonates |
JP3528997B2 (en) * | 1995-12-15 | 2004-05-24 | 日本ジーイープラスチックス株式会社 | Method for producing polycarbonate |
US5747609A (en) * | 1996-01-17 | 1998-05-05 | Asahi Kasei Kogyo Kabushiki Kaisha | Method for producing an aromatic polycarbonate having improved melt stability |
DE19609057A1 (en) * | 1996-03-08 | 1997-09-11 | Bayer Ag | Process for the preparation of diaryl carbonates and the polycarbonates obtainable therefrom |
AU3379397A (en) * | 1996-06-20 | 1998-01-07 | Nutrasweet Kelco Company, The | Food products containing bacterial cellulose |
DE10100404A1 (en) | 2001-01-05 | 2002-07-11 | Bayer Ag | Process for the production of polycarbonate |
CA2378922C (en) * | 2002-01-16 | 2009-01-27 | Rutgers, The State University Of New Jersey | Compositions and methods of making plastic articles from polymer blends containing polyethylene |
KR100813452B1 (en) * | 2003-08-21 | 2008-03-13 | 미쓰비시 가가꾸 가부시키가이샤 | Process for producing aromatic polycarbonate |
EP1657272B2 (en) * | 2003-08-21 | 2020-04-08 | Mitsubishi Chemical Corporation | Process for producing aromatic polycarbonate |
US7183371B2 (en) | 2004-11-01 | 2007-02-27 | General Electric Company | Method for making polycarbonate |
US7189869B2 (en) | 2004-11-01 | 2007-03-13 | General Electric Company | Method for making polycarbonate |
US7498399B2 (en) * | 2006-05-31 | 2009-03-03 | Sabic Innovative Plastics Ip B.V. | Method of preparing ester-substituted diaryl carbonates |
US20080071555A1 (en) * | 2006-08-29 | 2008-03-20 | Juergen Sattler | Application solution proposal engine |
US7547799B1 (en) | 2008-06-20 | 2009-06-16 | Sabic Innovative Plastics Ip B.V. | Method for producing phenolic compound |
DE102009024525A1 (en) | 2009-06-06 | 2010-12-16 | Bayer Materialscience Ag | Process for the preparation of phosgene from carbon monoxide and hydrogen chloride |
DE102009032020A1 (en) * | 2009-07-07 | 2011-01-13 | Bayer Materialscience Ag | Process for the production of polycarbonate |
ES2643234T3 (en) * | 2010-03-30 | 2017-11-21 | Covestro Deutschland Ag | Procedure for the preparation of diaryl carbonates and polycarbonates |
CN112221695B (en) * | 2020-09-28 | 2022-09-30 | 穆索诺伊矿业简易股份有限公司 | Copper separation and smelting combined copper extraction method for copper oxide ores with different oxidation rates |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4182726A (en) * | 1974-06-25 | 1980-01-08 | Snamprogetti, S.P.A. | Process for the preparation of aromatic carbonates |
US4452968A (en) * | 1981-11-30 | 1984-06-05 | General Electric Company | Synthesis of polycarbonate from dialkyl carbonate and bisphenol diester |
US5189139A (en) * | 1991-08-08 | 1993-02-23 | The Dow Chemical Company | Preparation of polycarbonates comprising separating bisphenol, converting bisphenol to diaryl carbonate and recycling |
-
1991
- 1991-08-08 US US07/741,925 patent/US5189139A/en not_active Expired - Lifetime
-
1992
- 1992-07-10 WO PCT/US1992/005800 patent/WO1993003084A1/en active IP Right Grant
- 1992-07-10 JP JP50357293A patent/JP3260369B2/en not_active Expired - Fee Related
- 1992-07-10 DE DE69211113T patent/DE69211113T2/en not_active Expired - Fee Related
- 1992-07-10 EP EP92915405A patent/EP0552331B1/en not_active Expired - Lifetime
- 1992-07-10 ES ES92915405T patent/ES2087545T3/en not_active Expired - Lifetime
- 1992-07-10 CA CA002092288A patent/CA2092288A1/en not_active Abandoned
- 1992-07-10 AT AT92915405T patent/ATE138671T1/en not_active IP Right Cessation
- 1992-08-07 CN CN92109238A patent/CN1069740A/en active Pending
-
1993
- 1993-02-22 US US08/020,502 patent/US5336750A/en not_active Expired - Lifetime
- 1993-04-07 KR KR1019930701056A patent/KR100214904B1/en not_active IP Right Cessation
Non-Patent Citations (1)
Title |
---|
No further relevant documents disclosed * |
Also Published As
Publication number | Publication date |
---|---|
ES2087545T3 (en) | 1996-07-16 |
WO1993003084A1 (en) | 1993-02-18 |
JP3260369B2 (en) | 2002-02-25 |
EP0552331A1 (en) | 1993-07-28 |
DE69211113T2 (en) | 1996-10-02 |
KR930702420A (en) | 1993-09-09 |
US5189139A (en) | 1993-02-23 |
DE69211113D1 (en) | 1996-07-04 |
CA2092288A1 (en) | 1993-02-09 |
EP0552331B1 (en) | 1996-05-29 |
US5336750A (en) | 1994-08-09 |
ATE138671T1 (en) | 1996-06-15 |
CN1069740A (en) | 1993-03-10 |
KR100214904B1 (en) | 1999-08-02 |
JPH06502215A (en) | 1994-03-10 |
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